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7500-Rn RADON*

7500-Rn A. Introduction

1. Occurrence and Significance 2. References

Radon-222 is a gaseous decay product of naturally occurring 1. PARTRIDGE, J.E., T.R. HORTON & E.L. SENSINTAFFAR. 1979. A Study of
radium-226. It is an alpha-emitter with a 3.82-d half-life, and Radon-222 Released from Water During Typical Household Activ-
normally is of concern only in groundwater. It is considered to be ities. ORP/EERF-79 1, Eastern Environmental Radiation Facility,
carcinogenic, as are its short-lived daughters. In household air, Montgomery, Ala.
radon may originate from radium in building materials and the 2. SMITH, B.M., W.N. GRUNE, F.B. HIGGINS, JR. & J.G. TERRILL, JR. 1961.
surrounding soil. Where radon concentration in the water supply Natural radioactivity in ground water supplies in Maine and New
is high, the water also can be a major source of radon in Hampshire. J. Amer. Water Works Assoc. 53:75.
household air. While radon dissolves readily in water and other 3. ALDRICH, L.K., III, M.K. SASSER & D.A. CONNERS, IV. 1975. Evalu-
solvents, it is easily displaced from water by air; thus, aeration of ation of Radon Concentrations in North Carolina Ground Water
Supplies. Dept. Human Resources, Div. Facility Services, Radiation
radon-bearing water in normal household uses can release a
Protection Branch, Raleigh, N.C.
significant fraction of the dissolved radon to the air.13
4. OCONNELL, M.F. & R.F. KAUFMAN. 1976. Radioactivity Associated
The average 222Rn concentration in community groundwater
with Geothermal Waters in the Western United States. U.S. Envi-
systems in the U.S. is estimated to range from 200 to 600 ronmental Protection Agency Technical Note ORP/LV-75-8A.
pCi/L,2 6 with some individual wells having much higher con- 5. DUNCAN, D.L., T.F. GESELL & R.H. JOHNSON, JR. 1976. Radon-222 in
centrations. potable water. In Proc. Health Physics Soc. 10th Midyear Topical
Symposium: Natural Radioactivity in Mans Environment.
*Approved by Standard Methods Committee, 2006.
6. COTHERN, C.R. & P.A. REBERS. 1990. Radon, Radium, and Uranium
Joint Task Group: 20th EditionStephen H. Pia (chair), Loren A. Berge, C. in Drinking Water. Lewis Publishers, Inc., Chelsea, Mich.
Richard Cothern, Paul B. Hahn, Vernon F. Hodge, Nancy E. Kinner, S. Kusum
Perera, George S. Uyesugi.

7500-Rn B. Liquid Scintillation Method

1. General Discussion is provided for selection of the analytical window to minimize


the background contribution to the measurement.
a. Principle: This method is specific for radon-222 (radon) in Some cocktails will become progressively quenched by atmo-
drinking water. Radon is partitioned selectively into a mineral- spheric oxygen after opening. This problem has not been noted
oil scintillation cocktail immiscible with the water sample. The for the mineral-oil-based cocktail. For other than mineral-oil-
sample is dark-adapted and equilibrated, and then counted in a based cocktails, check weekly for quenching.
liquid scintillation counter using a region or window of the Radon has an affinity for some plastics used in sample con-
energy spectrum optimal for radon alpha particles. Results are tainers. Use only glass sample containers or glass scintillation
reported as pCi/L. vials with TFE or foil-lined caps.
The procedure has been developed for the analysis of radon in c. Sample preservation, storage, and holding time: Collect
drinking water supplies from groundwater and surface-water samples from a nonaerated faucet that has been allowed to flow
sources. Applications of this analytical procedure to matrices for sufficient time so that the sample is representative of the
other than drinking water have not been studied; use caution in water in the distribution system or well. The following procedure
analyzing any such samples. will minimize the loss of radon from the sample during collec-
b. Interferences: There are no known chemical interferences tion:
from species found in drinking water nor from the dilute con- Place a glass sample vial in a 300- to 600-mL beaker or other
centration of acid that may be present in the calibration stan- suitable container; attach delivery tube to faucet, and start the
dards. Uranium, radium, or other radioactive elements would flow. Make sure that delivery tube does not let bubbles enter the
cause a positive bias, if present in quantities significantly greater sample. Fill vial to prevent its floating, then fill beaker until vial
than the radon. is submerged. Place tip of delivery tube about two thirds of the
Diffusion of radon is affected by temperature and pressure. Let way into vial and fill until approximately two or more vial
samples equilibrate to room temperature before processing. volumes (50 to 100 mL) have been displaced. Carefully remove
Precision and accuracy of the method are affected by the vial by hand or with a pair of 25-cm (10 in.) tweezers and cap
background in the energy window used for analysis. A procedure vial with a TFE or foil-lined cap. Cap sample vials underwater,

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RADON (7500-Rn)/Liquid Scintillation Method

if possible. Invert sample and check for air bubbles. If any equilibrium with radium-226. Determine optimal analytical
bubbles are present, discard sample and repeat sampling proce- window as outlined in 4b below. After ingrowth period, let
dure. sample dark-adapt for 3 h if necessary and count for 50 min.
Alternatively, collect samples in containers other than scintil- Repeat counting two additional times. From pooled results
lation vials, with similar precautions. calculate a system calibration factor by the following expres-
Record date and time of sample collection and store sample in sion:
a cooler. Transport samples to laboratory in a cooler or other
suitable insulated package to avoid large temperature changes
and outgassing of radon. Begin counting within 4 d or applicable S B
CF
regulatory specified holding time. C V
d. Minimum detectable concentration: 18 pCi/L for a 50-min
count time, 6 cpm background, 6 cpm/pCi calibration factor, and where:
energy region optimized by the procedure in 4b. CF calibration factor, cpm/pCi,
S standard counting rate, cpm,
B background counting rate, cpm,
2. Apparatus
C concentration of radium-226 standard, pCi/L, and
V volume of standard used, 0.015 L.
a. Pipet: 5-mL mechanical pipet or syringe.
b. Selecting optimal window: Count a radon standard for 5 min
b. Scintillation cocktail dispenser adjustable to deliver 5 mL.
or sufficient time to acquire several thousand counts or more in
c. Liquid scintillation counter: Preferably use a system per-
the alpha region and generate a sample spectrum. For greater
mitting automatic spectral analysis.
d. Faucet connector or universal faucet adapter. clarity use a log scale for the channel number or energy axis if
e. Plastic tubing for connector or adapter. possible.
f. Scintillation vials: 23-mL glass vials with caps, TFE or The alpha activity region of interest will be obvious as one
foil-lined. or two large peaks at the higher end of the energy spectrum.
g. Volumetric glassware. The lower peak is the doublet of radon-222 and polonium-218
h. Sample storage and shipping containers, insulated. and the higher peak is that of polonium-214. The optimal
window is formed by extending the region by approximately
10 channels on each side of the alpha peaks. Use this window
3. Reagents for subsequent calibration and analysis. Calibration factor
should be at least 6 cpm/pCi with the background not exceed-
ing 6 cpm.
a. Scintillation cocktail: Water-immiscible high-efficiency
mineral oil cocktail or other commercial equivalent. For counters not having a spectrum display, set window
b. Hydrochloric acid, HCl, conc. initially wide-open and count for sufficient time to obtain
c. Water, radon-free demineralized or equivalent. several thousand counts. Adjust energy window to a width of
d. Radium solution: Use two dilutions for calibration and 5% of full scale at upper end of scale (95 to 100%) and
check standards. Use NIST-traceable (explicit or implicit) radi- determine count rate in the region. Repeat counts at succes-
um-226 standard solution. sively lower regions using the same 5% interval (90 to 95, 85
to 90, 80 to 85, etc.). Plot count rate versus midpoint of
interval and choose region of interest, which will be evident
4. Procedure by one or two prominent peaks in the upper half of the energy
scale. Calibration factor should be at least 6 cpm/pCi with the
background not exceeding 6 cpm.
a. Calibration: Prepare 100 mL radium-226 in water stan-
c. Analysis of samples: Carefully remove by pipet 8.5 mL
dard such that the final activity will be approximately 8000
pCi/L by the procedure suggested below. Transfer standard to sample from the scintillation vial used for collection and add 5
a scintillation vial or other suitable container, seal, and record mL water-immiscible scintillation cocktail. Alternatively, pipet,
initial mass to nearest 0.0001 g. To a 100-mL volumetric flask without turbulence, a 15-mL portion to a scintillation vial con-
add 20 mL water and 0.5 mL conc HCl; stopper. Transfer with taining 5 mL cocktail if sample was collected in a different
a pipet, or suitable dropper, the required mass of radium container.
solution into flask; re-weigh vial. Obtain actual mass of Cap and shake sample for 30 s and set aside in the dark for a
radium solution added by difference of final and initial minimum of 3 h to equilibrate radon progeny and dark-adapt
weights. Fill to mark and mix. sample. Count all samples within the regulation specified hold-
Transfer 15 mL diluted standard into scintillation vial, to ing time. The time of sample collection is the initial time for
which has been added 5 mL mineral oil cocktail. Prepare at least decay correction.
three standards and three backgrounds using distilled or deion- Count a standard for 5 min or longer if required and either
ized water. The relative percent deviation spread of the resultant examine spectrum or compare results to previous standards to
calibration factors should be 5%. determine if there has been any shift or quench due to changes
Set standards and background samples aside for at least in the cocktail or instrument drift. Count samples for 50 min
25 d (99% ingrowth) to allow radon progeny to attain secular or to a percent 2 counting error of 10% or for a period of

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RADON (7500-Rn)/Liquid Scintillation Method

time to achieve an uncertainty in the net counting rate corre- these backgrounds to calculate results for batch. The background
sponding to program data quality objectives using optimized should be 6 cpm.
window settings for alpha counting. Make sure the expression For a suitable background sample, use laboratory deionized wa-
used includes the background in the uncertainty computation. ter, or prepare by boiling 2 L laboratory radium- and uranium-free
This may have to be done manually because most instruments tap water to remove residual radon if present. Store the cooled tap
calculate the uncertainty only for the gross counting rate. water in a capped 2-L bottle.
b. Duplicate samples: Collect duplicate field samples for one
out of every ten samples. Preferably collect all samples in
5. Calculations
duplicate if the number of samples from an individual client
represents a single source. Ensure that at least 10% of the
Calculate concentration of radon-222 in pCi/L from the fol- samples analyzed daily are duplicates, and that duplicate
lowing equation: analyses have a relative percent difference (RPD) less than
or equal to the percent 2 counting error or 10% of the
decay-corrected radon concentration, whichever is greater.
G B
Rn, pCi/L Relative percent difference is calculated by the following
CF D V expression:

where: Analysis 1 Analysis 2 200


RPD
G gross counting rate of sample, cpm, Analysis 1 Analysis 2
B background counting rate, cpm,
CF calibration factor (see 4a), Record the RPD and note acceptability of the duplicate anal-
V volume of sample (0.015 L), and ysis. If RPD exceeds the limits, recount duplicates. If results still
D decay factor for Rn-222 between time of collection and exceed limits but RPD for the quality control check standard is
midpoint of counting period for that sample. acceptable, a problem with the sampling procedure may exist.
Resolve problem before collecting and analyzing additional sam-
Calculate 2 (95% confidence level) counting uncertainty, as:
ples.
c. Quality control check standard (QCCS): QCCSs are prepared
2
G

TG TB
B

2, pCi/L CF D V
from a dilution of radium different from that used to prepare
standards and should have a nominal activity of 8000 pCi/L. Place
first QCCS immediately after first background and before first
sample. Place additional QCCS after every tenth sample in batch,
and final QCCS as last sample of the batch.
where: The relative percent difference (RPD) between sequential
TG duration of sample count, and pairs of QCCS samples must be less than or equal to the 2
TB duration of background count. counting error or 10% of the known value of the QCCS sample,
whichever is greater. If RPD exceeds this value, recount the pair
Report 2 uncertainty with each drinking water radioactivity
of QCCS samples. If RPD is still unacceptable, standards and/or
concentration result. This term represents the uncertainty due to
instrument are suspect. Resolve problem and rerun samples
the random nature of radioactive decay; it is related to count time
between suspect QCCS.
and can be used to determine whether sample was counted long
d. Records: Collect and maintain results from backgrounds,
enough to satisfy any required precision criteria. If percent
duplicate pairs, and QCCS standards in a bound notebook;
counting error (2 counting error divided by activity concentra-
include date, results, name of analyst, and comments relevant to
tion) exceeds precision requirements, count sample longer or
data evaluation.
reduce the holding time on re-collected samples.
Plot averages of backgrounds and QCCS standards on a con-
Report result and counting error together in the form:
trol chart for the counter.

X 2 pCi/L, 2 counting error 7. Precision and Bias

For example, for a water sample with calculated radon-222 A collaborative study of this method composed of 36 partic-
concentration of 285 pCi/L and 2 counting error of 27 pCi/L, ipants1 produced the results shown below:
report result as:
Sample Conc. Accuracy Repeatability Reproducibility Bias
pCi/L % pCi/L pCi/L %
222
Rn: 285 27 pCi/L, 2 counting error
111 101102 9 12 0.72.3
153 102103 10 1618 2.33.4
6. Quality Control
8. Reference
a. Background samples: Include a minimum of two back-
ground samples with each batch of 20 samples. Place back- 1. PIA, S.H. & P.B. HAHN. 1992. Radiation Research and Methods
grounds as first and next-to-last samples of batch. Use average of Validation Annual Report 1992. Environmental Monitoring Systems

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RADON (7500-Rn)/Liquid Scintillation Method

LaboratoryLas Vegas, Off. Research and Development, U.S. En- WHITTAKER, E.L., J.D. AKRIDGE & J. GIOVINO. 1987. Two Test Proce-
vironmental Protection Agency, Las Vegas, Nev. dures for Radon in Drinking Water. EPA/600/2 87/082, U.S. En-
vironmental Protection Agency, Las Vegas, Nev.
9. Bibliography VITZ, E. 1991. Toward a standard method for determining waterborne
radon. Health Phys. 60:817.
YOUDEN, W.J. & E.H. STEINER. 1975. Statistical Manual of the Associ- LOWRY, J.D. 1991. Measuring low radon levels in drinking water sup-
ation of Official Analytical Chemists. Assoc. of Official Analytical plies. J. Amer. Water Works Assoc. 83(4):149.
Chemists, McLean, Va. C OMMITTEE ON R ISK A SSESSMENT OF E XPOSURE TO R ADON IN
PRICHARD, H.M. & T.F. GESELL. 1977. Rapid measurements of Rn-222 DRINKING WATER, NATIONAL RESEARCH COUNCIL. 1999. Risk
concentrations in water with a common liquid scintillation counter. Assessment of Radon in Drinking Water. National
Health Phys. J. 33:577. Academy Press, Washington, D.C.

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